High refractive index liquids based on meta-substituted s-alkyl thioethers

Abstract

The present invention relates to liquid aromatic thioethers, a process for the preparation of the liquid aromatic thioethers, an article comprising the liquid aromatic thioethers as well as the use of the liquid aromatic thioethers as a component or substantial part of an optical liquid, window material, color filter, coating, varnish, lacquer, dye or pigment formulation, immersion liquid, calibration liquid or matching liquid, ingredient or additive in a plastic material or ingredient or additive in a polymer.

1 . A liquid aromatic thioether, satisfying formula A1, A2, A3, or A4: 
       
         
           
           
               
               
           
         
         wherein X′=Cl, Br, I, or X″, and 
         X″=S(CH 2 CHR1)-Z,
 wherein Z=C(O)G, C(O)A-G, or P(O)(OR2) 2 ,
 wherein G=H, Me, Et,  i Prop,  n Prop, or  t But, 
 A=O or NH, 
 R1=H or Me, and 
 R2=Me, Et,  n Prop, or  i Prop; 
 
 
       
       
         
           
           
               
               
           
         
         wherein X′=Cl, Br, I, or X″′, and 
         X″′=S(CH 2 CHR1)-Z′,
 wherein Z′ is as defined above,
 wherein each R1, R3, and R3′ is independently H or Me, 
 n=2 or 3, and 
 Y=H, Me, Et,  i Prop,  n Prop, or  t But; 
 
 
       
       
         
           
           
               
               
           
         
         wherein X′=I or Br, and 
         R4=a C1 to C8 linear or branched alkyl chain, a carbocycle with 5 or 6 C-atoms, or Z″ as defined above, wherein m and n are each independently 1, 2, or 3 and wherein one or two non-neighbouring ring-forming —CH 2 -moieties of Z″ are replaced by sulfur; and 
       
       
         
           
           
               
               
           
         
         wherein R4 and R5 are each independently a C1 to C8 linear or branched alkyl chain, a carbocycle with 5 or 6 C-atoms, or Z″ as defined above. 
       
     
     
         2 . The liquid aromatic thioether of  claim 1 , which satisfies formula A1 and is a reaction product of compounds of the following formulae A and B: 
       
         
           
           
               
               
           
         
         wherein, in formula A, X=Cl, Br, I, or SH; and 
         in formula B, Y=H, Me, Et,  i Prop,  n Prop, or  t But, and 
         Z=C(O)G, C(O)A-G, or P(O)(OR2) 2 ,
 wherein G=H, Me, Et,  i Prop,  n Prop, or  t But, 
 A=O or NH, and 
 R2=Me, Et,  n Prop, or  i Prop. 
 
       
     
     
         3 . (canceled) 
     
     
         4 . The liquid aromatic thioether of  claim 1 , which satisfies formula A2 and is a reaction product of compounds of the following formulae A1 and C: 
       
         
           
           
               
               
           
         
         wherein, in formula A1, X′=Cl, Br, I, or X″, and 
         X″=S(CH 2 CHR1)-Z
 wherein Z=C(O)G, G=H, Me, Et,  i Prop,  n Prop, or  t But, and 
 R1=H or Me; and 
 
         in formula C, n=2 or 3, and 
         R3 and R3′ are each independently H or Me. 
       
     
     
         5 . (canceled) 
     
     
         6 . The liquid aromatic thioether of  claim 1 , which satisfies formula A3 and is a reaction product of a compound of the following formula D and an alkylthiol HSR4: 
       
         
           
           
               
               
           
         
         wherein, in formula D, X=I, and 
         X′=Br or X=X′=I or Br; and 
         in the alkylthiol, R4=a C1 to C8 linear or branched alkyl chain, a carbocycle with 5 or 6 C-atoms, or Z″ as defined above, wherein m and n are each independently 1, 2, or 3 and wherein one or two non-neighbouring ring-forming —CH 2 -moieties of Z″ are replaced by sulfur. 
       
     
     
         7 . (canceled) 
     
     
         8 . The liquid aromatic thioether of  claim 1 , which satisfies formula A4 and is a reaction product of a compound of the following formula D and an alkylthiol HSR5: 
       
         
           
           
               
               
           
         
         wherein, in formula D, X=I, and 
         X′=Br or X=X′=I or Br; and 
         in the alkylthiol HSR5, R5=a C1 to C8 linear or branched alkyl chain, a carbocycle with 5 or 6 C-atoms, or Z″ as defined above, wherein m and n are each independently 1, 2, or 3 and wherein one or two non-neighbouring ring-forming —CH 2 -moieties of Z″ are replaced by sulfur, wherein and 
         R4 and R5 are the same or different. 
       
     
     
         9 . The liquid aromatic thioether of  claim 1 , which satisfies formula A4 and is a reaction product of a compound of the following formula A3 and Mg, wherein the reaction product is a Grignard reagent of formula A3, 
       
         
           
           
               
               
           
         
         wherein, in formula A3, X′=I or Br, and 
         R4=a C1 to C8 linear or branched alkyl chain, a carbocycle with 5 or 6 C-atoms, or Z″ as defined above, wherein m and n are each independently 1, 2, or 3 and wherein one or two non-neighbouring ring-forming —CH 2 -moieties of Z″ are replaced by sulfur; or 
         which satisfies formula A4 and is a reaction product of the Grignard reagent of A3 and R5SSO 3 M, 
         wherein M=Li or Na, and 
         R5=a C1 to C8 linear or branched alkyl chain, a carbocycle with 5 or 6 C-atoms or Z″ as defined above, wherein m and n are each independently 1, 2, or 3 and wherein one or two non-neighbouring ring-forming —CH 2 -moieties of Z″ are replaced by sulfur, wherein and 
         R4 and R5 are the same or different. 
       
     
     
         10 . The liquid aromatic thioether of  claim 1 , which has a refractive index in a range of from 1.50 to 1.9 and/or an Abbe's number in a range of from 25 to 110. 
     
     
         11 . A process for preparing the liquid aromatic thioether of  claim 1 , the process comprising:
 A) providing compounds of the following formulae A and B:   
       
         
           
           
               
               
           
         
         
           wherein, in formula A, X=Cl, Br, I, or SH, and 
           in formula B, Y=H, Me, Et,  i Prop,  n Prop, or  t But, and 
           Z=C(O)G, C(O)A-G, or P(O)(OR2) 2 .
 wherein G=H, Me, Et,  i Prop,  n Prop, or  t But, 
 A=O or NH; or 
 
         
         B) providing compounds of the following formulae A1 and C: 
       
       
         
           
           
               
               
           
         
         
           wherein, in formula A1, X′=Cl, Br, I, or X″, and 
           X″=S(CH 2 CHR1)-Z
 wherein Z=C(O)G, G=H, Me, Et,  i Prop,  n Prop, or  t But, and 
 R1=H or Me, and 
 
           in formula C, n=2 or 3, and 
           R3 and R3′ are each independently H or Me; or 
         
         C) providing a compound of the following formula D and an alkylthiol HSR4: 
       
       
         
           
           
               
               
           
         
         
           wherein, in formula D, X=I, and 
           X′=Br or X=X′=I or Br; and 
           in the alkylthiol, R4=a C1 to C8 linear or branched alkyl chain, a carbocycle with 5 or 6 C-atoms, or Z″ as defined above, wherein m and n are each independently 1, 2, or 3 and wherein one or two non-neighbouring ring-forming —CH 2 moieties of Z″ are replaced by sulfur; or 
         
         D) providing a compound of above formula D and an alkylthiol HSR5 or a compound of the following formula A3 and Mg and an alkylthiol R5SSO 3 M: 
       
       
         
           
           
               
               
           
         
         
           wherein, in formula A3, X′=I or Br, and 
           R4=a C1 to C8 linear or branched alkyl chain, a carbocycle with 5 or 6 C-atoms, or Z″ as defined above, wherein m and n are each independently 1, 2, or 3 and wherein one or two non-neighbouring ring-forming —CH 2 -moieties of Z″ are replaced by sulfur, and 
           M=Li or Na, and 
           in the alkylthiols HSR5 and R5SSO 3 M, each R5 is independently a C1 to C8 linear or branched alkyl chain, a carbocycle with 5 or 6 C-atoms or Z″ as defined above, wherein in and n are each independently 1, 2, or 3 and wherein one or two non-neighbouring ring-forming —CH 2 -moieties of Z″ are replaced by sulfur, and 
           R4 and R5 are the same or different; and 
         
         E) reacting the compounds provided in A), B), C), or D), to obtain the liquid aromatic thioether. 
       
     
     
         12 . An optical lens, an optical liquid, a wave guide material, a tiltable prism, a window material, a color filter, a coating, a varnish, a lacquer, a dye or pigment formulation, an immersion liquid, a calibration or matching liquid, an ingredient or additive in a plastic material, or an ingredient or additive in a polymer, comprising the liquid aromatic thioether of  claim 1  as a part or as an ingredient in at least one of its parts,
 wherein the optical lens may be a tuneable focus lens. 
 
     
     
         13 . (canceled) 
     
     
         14 . The liquid aromatic thioether of  claim 1 , which satisfies formula A1. 
     
     
         15 . The liquid aromatic thioether of  claim 1 , which satisfies formula A2. 
     
     
         16 . The liquid aromatic thioether of  claim 1 , which satisfies formula A3. 
     
     
         17 . The liquid aromatic thioether of  claim 1 , which satisfies formula A4.